Production of branched chain hydrocarbons



Feb. 12, 1946. w E. ROSS 2,

' PRODUCTION OF BRANCHED CHAIN HYDROCARBONS FiledNOV. 24, 1942Fracfionai-ors Caralgst Scrubber lnverfior: WiNiam E. 2o

Patented Feb. 12,

HYDROCARBONS William E. Boss,'Berkeley, cane, acsignor to ShellDevelopment Company, San Francisco,

Calif., a corporation of Delaware Application November 24, 1942, SerialNo. 466,799 lsclaims. (o1. zoo-seas) This invention relates to theproduction of branched chain hydrocarbons;

An object of the invention is the provision of a more eflicient andeconomical process for the production of branched chain hydrocarbonsfrom straight chain paramn and olefin hydrocarbons. Another object ofthe invention is the provision of a process for the more eiilcientproduction of branched chain saturated hydrocarbons from saturatedhydrocarbons comprising open chain saturated hydrocarbons andunsaturated hydrocarbons comprising ethylene. Still another object ofthe invention is the provision of a process for the more eflicientproduction of 2,3-dimethyl butane' from saturated hydrocarbon fractionscomprising butane and unsaturated hydrocarbon fractions comprisingethylene.

Methods whereby the straight chain paraflln and olefin hydrocarbons,particularly the lower boiling of these hydrocarbons, abundantlyavailable in the petroleum industry, can be processed to obtain as themajor product a single hydrocarbon of branched structure or a mixture ofbranched chain hydrocarbons having the same number of carbon atoms tothe molecule, are often greatly desired. The use of processes whereinhydrocarbon cracking is the principal reaction is, in such cases,unsuited since the materials treated are converted to a wide-range ofhydrocarbons of which but a relatively small part I may comprise thedesired branched chain hydrocarbons. Resort is therefore often had tothe treatment of these materials under non-cracking conditions efiectingthe conversion of the open chain paramnic'hydrocarbon to a branched or amore highly branched chain product and the combining of the resultingbranched chain product with an available olefin hydrocarbon to obtain adesired branched chain product of higher molecular weight than thestarting materials. Utilization of several catalysts of entirelydifferhydrocarbons to branched or more highly branched chain paramnhydrocarbons comprise those of the molten salt type consisting of moltenmixtures of halide salts at least one of which is found that the degreeto which the catalyst melt is adversely aifected is substantiallyproportional to the amount of spent or partly spent catalyst ent nature,and the consequent increase in oper-- Catalysts particularly eflicientin their ability to catalyze the conversion of open chain parailln .thehighly desirable 2,3-dimethyl butane.

components in the body of the entire melt. and that removal of thesespent components substantially as rapidly as formed results in themaintenance of exceedingly high catalyst activity over longer periods ofoperation. The catalyst components, which are at least partly spent withrespect to their ability to catalyze the hydrocarbon isomerizationreaction, may be removed from the catalyst melt efliciently within thesystem by scrubbing the molten catalyst with incoming hydrocarbon feed,thereby separating a fluid catalyst residue, comprising the spent orpartially spent catalyst components, from active catalyst components.Such continuous and thorough scrubbing of the catalyst melt, however,results in a relatively rapid removal of catalyst components from thesystem, thereby considerably increasing the cost of operation. It hasnow been found that the 'fluid catalyst residue comprising the spentcatalyst components thus removed in the sombbing operation, to which asmall proportion of fresh aluminum chloride has been preferably added,can be used advantageously to efiect the reaction between branched chainsaturated hydrocarbon and olefinic hydrocarbons. The fact that the fluidcatalyst residue produced as a byproduct in the isomerization of asaturated hydrocarbon can be utilized as a catalyst in a subsequentalkylation of branched chain hydrocarbons thus brings within the realmof economic feasibility a novel and exceedingly eflicient process forthe production of branched chain hydrocarbons of higher molecular weightthan the starting materials. However, a still more advantageous featureof such a process resides in the fact that the inherent characteristicsof the fluid catalyst residue thus obtained as a by-product in theisomerization of paraflinic hydrocarbons enables the eflicientalkylation of isoparafllns with ethylene. Thus, isobutane can-bealkylated with ethylene in its presence to a product consisting mainlyof The fluid catalyst residue obtained as a by-product in theisomerization of saturated hydrocarbons. to

which a small amount of aluminum chloride has preferably been added toenhance its activity, thus presents a distinct advantage over theutilization of alkylation catalysts, such as, for example, sulfuricacid, which are found to be impractical for the alkylation ofisoparaflins with ethylene, and over the hydrocarbon-aluminum chloridecomplex sludge type catalysts, such as the complexes formed by reactingaluminum chloride with toluene or a kerosene extract, which are renderedun-' is a halide of the Friedel-Crafts type, in a first reaction zone,thereby eifecting the conversion of straight chain paraffin hydrocarbonsto branched chain parafiin hydrocarbons. A portion of the catalyst meltis continuously passed from the first reaction zone into a scrubbingzone wherein it is scrubbed with incoming hydrocarcatalyst residue,which comprises catalyst components at least partially spent withrespect to their ability to catalyze the hydrocarbon isomerizationreaction, is separated from active soluble catalyst components. The feedcontaining dissolved catalyst components is passed to the first reactionzone. A part or all of the hydrocarbon products comprising branchedchain paraflin hydrocarbons emanating from the first reaction zone isadmixed with olefin hydrocarbons from an outside source. The resultingmixture of hydrocarbons is contacted under alkylating conditions in asecond reaction zone with the fluid catalyst residue separated in thescrubbing zone, and

to which a small amount of fresh Friedel-Crafts type halide has beenpreferably added, thereby alkylating branched chain parafiins witholefins. Products from the second reaction zone are fractionated toseparate a product comprising branched chain hydrocarbon reactionproduct therefrom.

In order that the invention may be more fully set forth and morereadily. understood, reference is made to the single drawingaccompanying and forming part of this specification. The single figurein the drawing is a more or less diagrammatic elevational view of oneform of apparatus suitable for executing the invention.

An isomerizable saturated hydrocarbon such as, for example, butane fromany suitable source is forced by means of pump I through valved line 2into an intermediate part of an extraction zone. The extraction zone mayconsist of a column 3 provided with suitable packing material, bafflesor the like. Within extraction column3 the butane is contacted in theliquid phase with a portion of the catalyst emanating from the reactionzone as described more fully below. Liquid butane comprising extractedcatalyst components is passed from extraction column 3 through valvedline 4 and heater 5 into a reaction zone. The reaction zone may consistof a suitable reactor 6 provided with stirring means I and a separatingchamber 8. Although but one such reactor is shown within the drawing, itis to be understood that a plurality of such reactors, connected inseries or in parallel, may be used. Within reactor 6 the butane iscontacted with a suitable isomerization catalyst of the molten salttype. Such catalysts comprise mixtures of molten halide salts, at leastone of which is a halide of the Friedel-Crafts type. A particularlyemcient isomerizatlon catalyst comprises, for example, a molten mixtureof an antimony halide and an aluminum halide. A molten mixture of AlClaand SbCla, containing from about 3 to 24 mol percent of aluminumchloride and modified, if desired, by the presence of ahalide of'analkali or an alkaline earth metal, is highly suitable It is to beunderstood, however, that the invention is in no wise limited to but onespecific cata ly'st of the molten salt type, and other catalyst ing amixture of halide salts, at least one of which melts may be employedsuch as, for example, any of the following molten mixtures: aluminumchloride-sodium chloride-potassium chloride, aluminum chloride-sodiumchloride-zinc chloride, aluminum chloride-sulfur dioxide-zinc chloride,aluminum chloride-sodium chloride-potas-. sium chloride-zinc chloride,etc. A part or all of the halide components of the catalysts may bonfeed. Within the scrubbing zone a fluid comprise halides other than thechlorides, for

example, the bromides. V

The temperature to be maintained about 80- C. to about 200 C.,-andiscontrolled preferably executed in the presence of a hydrogen byjudicious heat input into heater 5. and, if

needed, by additional heating means-not shown I in the drawing. Theisomerization reaction is halide such as, for example, hydrogenchloride.

in the vapor or liquid phase. in the liquid phase, a pressure atleastsufliciently high is maintained within reactor 6 to keep at least asubstantial part of the butane in the liquid phase. v

Within separation chamber 8 a substantial de-- 7 gree of separationbetween catalyst melt and hydrocarbon will be eflected- The supernatenthy,-.

drocarbon layer, which in general will comprise some admixed anddissolved catalyst, is withdrawn from separator 8 and passed throughline 9 into a vaporizing zone,- The vaporizing zone may suitably consistof the lower part of a colum'n l2, an intermediate part of which isprovided with suitablepacking means, baflles, or the like. Within columnI 2 separation of hydrocarbons from entrained catalyst components isef-,

fected with the aid of heating coil l3. Since antimony' chloride isrelatively volatile, its separation from the hydrocarbon within column12 is aided by the introduction of cold hydrocarbon reflux into theupper part of the column by means of valved line l4. Vapors comprisingisobutane,

, unconvertednormalbutane and hydrogen chloto effect the condensation ofbutanes. Catalyst ride promoter are passed from the upper part of columnI! through line l6 and cooler l1 into ac-v cumulator 18. In passingthrough cooler II the stream is cooled to atemperature sufliciently'lowcomponents consisting essentially of antimony within re I salt by meansoiv'alved a soaeio conduit 22. The catalyst phase,,separated out withinseparator 8, is forced by means of pump 23 through line 24 into theupper part of extraction column 3. The portion of catalyst thus. introduced into extraction column 3 will pass countercurrent to the upflowof the liquid hydrocarbon. In its Passage through column 3 a portion ofcatalyst comprising antimony chloride is dissolved in the hydrocarbonstream and,

passed therewith to reactor 8. Another portion of the catalystcomprising components which are spent, or at least partly spent, withrespect to their ability to catalyze the isomerization reaction, remainsinsoluble in the hydrocarbon stream and is'separated therein as aheavier fluid catalyst residue. The hydrocarbon charge to the system ispreferably preheated, for example, with the aid of a suitable heatexchanger I I, to a temperature favorable to the extraction operation.This temperature will vary with the nature of the material being treatedand the particular catalyst used. In the treatment of paramnichydrocarbons temperatures in the approximate range of from 50 C. to 125C. and preferably from 50 C. to 100 C. are found suitable. The pressurewithin column 3 is always suiflciently high to maintain at least asubstantial portion of the hydrocarbon stream passing th'erethrough inthe liquid phase.

It has been found that the fluid catalyst residue separated withinextractor 3 will comprise any hydrocarbon-aluminum chloride complexformed within reactor 6. It has also been found that this material issubstantially insoluble in the hydrocarbon feed which contributed to itsformation and willnot undergo decomposition or disintegration to anysubstantial degree in the extraction zone, whereas the still activeantimony chloride-aluminum chloride catalyst possesses anappreciabledegree of solubility in the normal butane. The composition ofthe fluid catalyst residue separated within column 3 will vary to somedegree with the nature of material treated and operating conditionsused. The catalyst residue thus obtained as a by-product of theisomerization operation is found to possess appreciable fluidity andwill maintain this fluidity at temperatures substantially below roomtemperatures. The lower part of column may, however, be provided with ajacket for the passage of a heating medium therethrough to aid inmaintaining the desired temperature conditions therein.

The rate at which catalyst is withdrawn from separating chamber 8 andpassed to the upper part of extractor may vary within the scope of theinvention. As pointed out above, however, it is highly advantageous toeffect the catalyst withdrawal-at a rate sufllciently great to preventthe accumulation to any substantial degree of even partially spentcatalyst within the reactor.

From accumulator l8 liquid comprising 150- butane and normal butane isforced by means of pump 26 through line 21 into a stripping column 28.Gases and vapors, separately withdrawn from accumulator l8, are forcedby means of compressor 29 through line 30 into stripping column 28.Within stripping column 28 the hydrogen chloride promoter is separatedfrom the .hydrocarbon material, and removed therefrom through valvedline 3|. A portion or all of the hydrogen halide promoter passingthrough line 3| is recycled throughvalved line III to the reaction zone.Make-up hydrogen chloride is introduced into line Hi from an outsidesource through valved line 32. A liquid fraction comprising normalbutane and isobutane is passed through valved lines I! and 84 into afractionator 85. Within fractionator 25 a liquid fraction comprisingnormal butane is separated from a vapor fraction comprising isobutane.The liduid fraction is withdrawn from column I! through valved line 24and passed in part or in its entirety through valved line 21 to theisom- .erlzation zone. The vapor fraction is removed overhead fromcolumn ll through valved line 22.

The fluid catalyst residue separated within extraction column 2 iswithdrawn therefrom through valved line 4| and passed to a secondreaction zone. A small amountof fresh aluminum chloride is preferablyadded thereto by passing a part or all of the stream through a vesselcontainin anhydrous A101: or by addition of the halide salt throughvalved conduit 41. The amount of fresh aluminum chloride added to thefluid catalyst residue may vary within the scope of the invention inaccordance with the particular materials treated, composition of theisomerization catalyst, operating conditions, etc. Addition of freshaluminum chloride in amounts ranging from exceedingly small .amounts,for example.

about one percent, to substantially larger proportions up to, forexample, about twenty percent of the resulting catalyst mixture, issuitable. Greater or lesser amounts may be added, however, as occasionrequires without adversely affecting that peculiar quality of theresulting mixture which is imparted thereto by the inherentcharacteristics of the by-product catalyst residue emanating fromscrubber 3. If desired, a Friedel-Crafts type halide other than aluminumchloride, and even diflering from that utilized in the melt in reactor6, may constitute the fresh portion of the catalyst component added tothe catalyst residue passing through line 4|. The second reaction zonemay consist of a reactor 42 provided with suitable stirring means 43 anda suitable separating chamber, for example, a separating chamber 44 incommunication with the rest of the reactor in such wise that liquid mayflow therefrom by gravity into the reactor proper. Although but one suchreactor is shown in the drawing, one

or more reactors connected in series or in parallel may be used.

A part or all of the isobutane passing through line 38 is forced bymeans of pump .45 through line 48 intoline 4| leading into reactor 42.If desired, additional hydrocarbons comprising branched chain saturatedhydrocarbons may be drawn from an outside source and introduced intoline 46 by means of valved line 48. A substantially olefinic hydrocarbonfraction such as, for example, a fraction predominating in ethylene isintroduced from an outside source through valved line 49 into line 48.Within reactor 42 able indirect heat exchanger SI and other means notshown in the drawing. An excess of paraiflns with respect to oleflns ismaintained within reactor 42. Thus. the ratio of paraflins to oleflnsmay be as high as 4: 1 and even higher, if desired.

The presence of a hydrogen halide is found advantageous to thealkylation reaction, smaller amounts of hydrogen-halide being, ingeneral, required within reactor 42 then in reactor 6. Thus,

an amount of hydrogen chloride not substantially in. excess of about onepercent, for example, less than 0.5 percent, of the hydrocarbon chargeto reactor 42 has been found suitable. Higher proportions may, however,be'used. The hydrogen halide promoter supplied to reactor 42 'need notnecessarily be the same halide as that introduced into reactor 6.

Within separator 44 separation of hydrocarbons from the catalyst iseifected. The catalyst which separates as a lower layer flows back intoreactor 42. Spent catalyst in the form of a sludge is removed fromreactor 42 through valved line 52.

The spent sludgy material thus eliminated through line 52 may be treatedto recover AlCla therefrom by means not'shown in the drawing. Suchrecovery means may comprise the more drastic means involvingdistillation or heating to effect decomposition of the aluminumchloridehydrocarbon complex contained therein. From separator 44 asupernatant hydrocarbon layer comprising the desired alkylate, unreactedolefins and parafllns, and hydrogen halide promoter are passed throughvalved line 53 into a fractionator 54. Within fractionator 54 a lighterfraction comprising hydrogen chloride, unconverted-ethylene andisobutane is separated and removed therefrom through valved line 55.This lighter fraction is passed in part or in its entirety from prising2,3-dimethyl butane is withdrawn from fractionator 6| through valvedline 64 as a final product.

If desired, all of the hydrocarbon product removed as a liquid fractionfrom fractionator 28 and comprising both normal and isobutane may bepassed directly, by judicious manipulation of valves 65 and 66, intoline 46 leading to reactor 42.

It is to be pointed out that the invention is in no wise limited to theproduction of branched chain hydrocarbons from starting materialsconsisting of a paraffin and an olefin which is lower boiling than theparaffin. When the olefin introduced into the system is heavier thanthe. paraffinic hydrocarbons passed into reactor 42, unreacted branchedchain paraflin hydrocarbons are recycled together with the hydrogenchloride promoter to the alkylation zone through lines 55 and 56.Remaining reaction products, comprising the desired branched chainalkylate, unreacted olefin and some normal paraflins, are

fractionated in fractionator 6| to separate the to pass at least a partof the lighter fraction comprising the hydrogen halide promoterseparated within fractionator 54 to accumulator l8.

. may be accomplished by passing the overhead cumulatpr l8 throughvalved line H and passed in part .or in their entirety through valvedlines I2, "I, 58, 56 and into reactor 42.

This

Although the process of the invention has been described in itsapplication to the production of a branched chain hydrocarbon fractioncomprising 2,3-dimethyl butane from normal butane and ethylene, it is tobe understood that the in vention is in no wise liinited to the use ofthese particular hydrocarbons as the starting materials. Any saturatedhydrocarbon capable of bel ing isomerized to a branched or more highlybranched chain saturated hydrocarbon may constitute the saturatedhydrocarbon charge to the system. It need not necessarily be a purehydrocarbon and may have admixed therewith one or execution of thereaction. Particularly-desirable saturated hydrocarbon startingmaterials comprise fractions such as the butane, pentane,

hexane, etc., fractions obtained by fractional distillation of naturalor straight run gasoline or saturated hydrocarbon mixtures from anyother sources. A saturated hydrocarbon mixture of considerably widerboiling range, which may coinprise a substantial portion or all of thehydrocarbons boiling within the gasoline range, such as a naturalgasoline, casinghead gasoline or the like may. constitute the saturatedhydrocarbon charge to the system. In passing through the lsomerizationstage of the process substantial proportions of branched chainhydrocarbons are produced. The resulting isomerizate may be passed inpart or in its entirety to the alkylation zone. It may be desirable topass only a lower boiling fractionof the isomerizate to thealkylaethylene-containing fractions in the production of a branchedchain hydrocarbon product. The invention is, however, not limited to theuse of ethylene or ethylene-containing fractions as the olefinic chargeto the process. Other olefins or olefinic fractions, such as thosecomprising, for example, propylene, butylene, amylene, cyclo- .pentene,cyclohexene, or higher olefins, may be used. The olefin may be chargedto the alkylation zone in admixture with paraflinic hydrocarbons, thusenabling the use of ethane-ethylene,

fractionator 6| through valved lines 63 and 61 into a fractionator 68wherein the paraflinsare invention.

aluminum chloride to said catalystresiduepsepstantial amount of ethane.such as, for example, an ethane-ethylene fraction, is charged to thealkylation zone, ethane is preferably removed from the hydrogenchloride-containing fraction separated from the eilluence oi thealkylation reactor before this fraction is recycled thereto. This may beaccomplished by diverting all or a part of the stream flowing throughline 55 through valved line 13, and subjecting it to any suitabletreatment for the separation of ethane therefrom by means not shown inthe drawing,

arating isobutane from the eiiiuence of the first reaction zone,contacting said isobutane together and returning the substantiallyethane-free iraction comprising hydrogen chloride to reactor 42. Themeans utilized for effecting the separation of ethane may comprise suchsteps as distillation scrubbing with suitable absorbents for hydrogenchloride, etc. i

The process of the invention thus enables the eiiicient and highlyeconomical production of a wide variety of branched chain hydrocarbonfractions optionalLv predominating in branched chain hydrocarbons or thesame number of carbon atoms, with a minimum of operative steps, a highlevel of catalyst activity and maximum utilization of catalystcomponents charged to the system.

It is to be understood that the apparatus shown K may be modified asapparent to one skilled in the art without departing from the scope ofthe Thus for the sake of clarity parts of apparatus such as, forexample, certain additional heating means, iractionator reboilers,condensers, means for providing reflux to fractionators, accumulators,catalyst storage means, valves and the like have been omitted from thedrawing.

Example Butane was treated in the isomerization reactor amount or 4 to5% by weight of the butane charged was introduced into the reactor.Catalyst melt was passed from the reactor to the scrubber and scrubbedtherein with incoming butane at a rate sumciently high to preclude thepresence to any substantial degree of spent catalyst components withinthe reactor. The conversion of butane to isobutane was maintained at 4per pass. The isobutane product and fluid catalyst residue separated outin the scrubber were introduced into the alkylation reactor. A

fresh portion or A10]: in the amount of 17% by weight of the resultingmixture was added to the fluid catalyst residue entering the alkyiationreactor. Ethylene was introduced into the alkylation reactor at a rateproviding a mol ratio of isobutane to ethylene 0i 3 to 1. With a,contact time of 20 minutes and a temperature of 25 C. the hydrocarboneiliuence of the alkylation reactor contained 25% by weight 01' hexanesconsisting predominantly of 2,3-dimethyl butane.

I claim as my invention:

l. A process for the production or 2,3-dimethyl butane which comprisescontacting normal butane with a catalyst melt comprising aluminumchloride and antimony chloride at isomerizing conditions in a firstreaction zone thereby convetting normal butane to isobutane,continuously removing a portion oi the catalyst melt from the firstreaction zone, contacting said portion of catalyst melt with butanepassing to the flrst reaction zone thereby separating active catalystcomponents from a fluid catalyst residue, adding with added ethylene atalkylating conditions with said aluminum chloride-containing catalystresidue in a second reaction zone thereby reacting isobutane withethylene to form a branched chain hydrocarbon alkylation productcomprising 2,3- dimethyl butane, and separating hydrocarbons comprisingsaid 2,3-dimethyi butane from the effluence of the second reaction zone.

2. In a process for the production of branched chain hydrocarbons, thesteps which comprise contacting normal butane with a catalyst meltcomprising aluminum chloride and antimony chloride at isomerizingconditions in a first reaction zone thereby converting normal butane toisobutane, continuously removing a portion of the catalyst melt from thefirst reaction zone, contacting said portion of catalyst melt withbutane passing to the first reaction zone thereby separating activecatalyst components from a fluid catalyst residue, adding aluminumchloride to said catalyst residue, separating isobutane from theeiiiuence of the first reaction zone, contacting said aratinghydrocarbons comprising said alkylation product from the efliuence oithe second reaction zone.

3. In a process for the production of branched chain hydrocarbons, thesteps which comprise contacting saturated hydrocarbons comprising anopen chain saturated hydrocarbon with a catalyst melt comprisingaluminum chloride and antimony chloride at isomerizing conditions in afirst reaction zone thereby converting straight or branched chainsaturated hydrocarbons to branched or more highly branched chainsaturated hydrocarbons, continuously removing a. portion of the catalystmelt from the first reaction zone, contactmg said portion of catalystmelt with said saturated hydrocarbons passing 'to the first reactionzone thereby separating active soluble catalyst components from a fluidcatalyst residue, adding aluminum chloride to said catalyst residue,contacting at least a portion of the efliuence form a branched chainhydrocarbon alkylation product, and separating hydrocarbons comprisingsaid allwlation product from the eflluence oi the second reaction zone.

4. In a process for the production of branched chain hydrocarbons, thesteps which comprise contacting saturated hydrocarbons comprising anopen chain saturated hydrocarbon with a catalyst melt comprisingaluminum chloride and an- .timony chloride at isomerizing conditions ina first reaction zone thereby converting straight or branched chainsaturated hydrocarbons to branched or more highly branched chainsaturated hydrocarbons, continuously removing a portion of thecatalystmelt from the first reaction zone, contacting said P rtion ofcatalyst melt with saturated hydrocarbons passing to the first reactionzone thereby separating active soluble catalyst components from a fluidcatalyst residue, adding aluminum chloride to said catalyst resi .due,contacting at least a portion of the efliuence of the first reactionzone comprising branched chain hydrocarbons together with an addedhydrocarbon fraction predominating in a' straight conditions in a firstreaction zone thereby converting normal butane to isobutane,continuously removing a portion of the catalyst mel from the firstreaction zone, contacting said portion of catalyst melt with butanepassing vto the first reaction zone thereby separating active catalystcomponents from a fluid catalyst residue, adding aluminum halide to saidcatalyst residue, separating isobutane from the eflluence of the firstreaction zone, contacting said isobutane together with added ethylene atalkylating conditions with said aluminum halide-containing catalystresidue in a second reaction zone thereby reacting isobutane withethylene to form a branched chain hydrocarbon alkylation product, andseparating hydrocarbons comprising said alkylation product from theefiluence of the second reaction zone.

6. In a process for the production of branched chain hydrocarbons, thesteps which comprise contactingsaturated hydrocarbons comprising an openchain saturated hydrocarbon with a catalyst melt comprising a-moltenmixture of halide salts at least one of which is a halide of aluminum atisomerizing conditions in a first reaction zone thereby convertingstraight or branched chain saturated hydrocarbons to branched or morehighly branched chain saturated hydrocarbons, continuously removing aportion of the catalyst melt from the first reaction zone, contactingsaid portion of catalyst melt with said saturated hydrocarbons passingto the first reaction zone thereby separating active catalyst componentsfrom a fluid catalyst residue, adding aluminum halide to said catalystresidue, contacting at least a portion of the efliuence of the firstreaction zone comprising saturated branched chain hydrocarbons togetherwith added ethylene at alkylating conditions with said aluminumhalide-containing catalyst residue in a second reaction zone therebyreacting saturated branched chain hydrocarbons with ethylene to form abranched chain hydrocarbon alkylation product, and separatinghydrocarbons comprising said alkylation product from the eflluence ofthe second reaction zone.

7. In a process for the production of branched chain hydrocarbons, thesteps which comprise contacting saturated lnrdrocarbons comprising anopen chain saturated hydrocarbon with a catalyst melt comprising amolten mixture of halide salts at least one of which is a halide ofalumi-' num at isomerizing conditions in a first reaction zone therebyconverting straight or branched chain saturated hydrocarbons to branchedor more highly branched chain saturated hydrocarbons, continuouslyremoving a portion of the catalyst melt fromthe first reaction zone,contacting said portion of catalyst melt with saturated hydrocarbonspassing to the first reaction zone thereby separating active catalystcomponents from a fluid catalyst residue, adding aluminum halide to saidcatalyst residue, contacting at least a portion of theeffluence of thefirst reaction zone comprising branched chain saturated hydrocarbonstogether with an added hydrocarbon fraction predominating in 'a'straight chain olefin at alkylating conditions with said aluminumhalide-containing catalyst residue in a second reaction zone therebyreacting branched chain saturated hydrocarbons with said olefin to forma branched chain hydrocarbon alkylation product, and separatinghydrocarbons comprising said alkylation product from the efiiuence of lthe second reaction zone. y

8. In a process for the production of branched chain hydrocarbons, thesteps which comprise contacting normal butane with a catalyst meltcomprising a molten mixture of halide salts at least one of which is ahalide of .the Friedel- Crafts type at isomerizing conditions in a firstreaction zone thereby converting normal butane to isobutane,continuously removing a portion of the catalyst melt from the firstconversion zone, contacting said portion of catalyst melt with butanepassing to the first reaction zone thereby separating active catalystcomponents from a fluid catalyst residue, adding a fresh portion of saidhalide of the Friedel-Crafts type to said catalyst residue, contactingat least a part of the 'efliuence of the first conversion zonecomprising isobutane together with added ethylene at alkylatingconditions with said Friedel-Crafts type halide-containing catalystresidue in a second reaction zone thereby reacting isobutane withethylene to form a branched chain hydrocarbon alkylation product, andseparating hydrocarbons comprising said alkylation productfr'om thecffluence of the second reaction zone.

9. In a process for the production of branched chain hydrocarbons, thesteps which comprise contacting saturated hydrocarbons comprising anopen chain saturated hydrocarbon in admixture with a promoting amount ofa hydrogen halide with a catalyst melt comprising a molten mixture ofhalide salts at least one of which is a halide of the Friedel-Craftstype at isomerizing conditions in a first reaction zone therebyconverting straight or branched chain saturated hydrocarbons to branchedor more highly branched chain saturated hydrocarbons, continuouslyremoving a portion of the catalyst melt from the first conversion zone,contacting said portion of catalyst melt with saturated hydrocarbonspassing to the first reaction zone thereby separating active catalystcomponents from a fluid catalyst residue, adding a fresh portion of saidFriedel-Crafts type halide to said catalyst residue, contacting at leasta portion of the effiuence of' the first reaction zone comprisingsaturated branched chain hydrocarbons together with added ethylene atalkylating conditions with 1 said Friedel-Crafts type halide-containingcatalyst residue in a second reaction zone thereby reacting saturatedbranched chain hydrocarbons with ethylene to form a branched chainhydrocarbon alkylation product, and separating hydrocarbons comprisingsaid alkylation product from the efliuence ofthe second reaction zone.

10. In a process for the production of branched chain hydrocarbons, thesteps which comprise contacting saturated hydrocarbons comprising anopen chain saturated hydrocarbon with a catalyst melt comprising amolten mixture of halide salts at least one of which is a halide of theFriedel-Crafts type at isomerizing conditions in a first reaction zonethereby converting straight or branched chain saturated hydrocarbons tobranched or more highly branched chain saturated hydrocarbons,continuously removing a portion of the catalyst melt from the firstreaction zone, contacting said portion of catalyst melt with saturatedhydrocarbons passing to the first reaction zone thereby separatingactive catalyst components from a fluid catalyst residue, adding aFriedel-Crafts type halide to said catalyst residue, contacting at leasta portion of the effiuence of the first reaction zone comprisingsaturated branched chain hydrocarbons together with an added hydrocarbonfraction containing straight chain paraffins and olefins at alkylatingconditions with said Friedel-Crafts type halidecontaining catalystresidue in a second reaction zone thereby reacting saturated branchedchain hydrocarbons with said olefins to form a branched chain alkylationproduct, separating a fraction comprising said alkylation product and afraction Comprising straight chain paraifins from the efiiuence of thesecond reaction zone, and passing said fraction comprising straightchain parafiins to said first reaction zone.

11. In a process for the production of antiknocl; motor fuels, the stepswhich comprise contacting a hydrocarbon mixture predominating insaturated straight chain hydrocarbons and boiling within the gasolineboiling range with a catalyst melt comprising aluminum chloride andantimony chloride at isomerizing conditions in a first reaction zonethereby effecting the conversion of straight chain saturatedhydrocarbons to branched chain saturated hydrocarbons, continuouslyremoving a portion of the catalyst melt from the first reaction zone,contacting said portion of catalyst melt with said hydrocarbon mixurepassing to the first reaction zone thereby separating active solublecatalyst components from a fluid catalyst residue, adding aluminumchloride to said catalyst residue, and contacting at least a part of theefiluence of the first reaction zone comprising branched chain saturatedhydrocarbons together with added ethylene at alkylating conditions withsaid aluminum chloride-containing catalyst residue in a second reactionzone thereby reacting saturated branched chain hydrocarbons withethylene.

12. In a process for the production of antiknock motor fuels, the stepswhich comprise contacting a hydrocarbon mixture predominating insaturated straight chain hydrocarbons and boilingwithin the gasolineboiling range with a catalyst melt comprising aluminum chloride andantimony chloride at isomerizing conditions in a first reaction zonethereby effecting the conversion of straight chain saturatedhydrocarbons to branched ,chain saturated hydrocarbons, continuouslyremoving a portion of the catalyst melt from the first reaction zone,contacting said portion of catalyst melt with said hydrocarbon mixturepassing to the first reaction zone thereby separating active catalystcomponents from a fluid catalyst residue, adding aluminum chloride tosaid catalyst residue, and contacting at least a part of the affluenceof the first reaction zone comprising branched chain saturatedhydrocarbons together with an added hydrocarbon fraction predominatingin olefinic hydrocarbons at alkylating conditions with said aluminumchloride-containing catalyst residue in a second reaction zone therebyreacting branched chain hydrocarbons with said olefinic hydrocarbons.

13. In a process for the production of antiknock motor fuels, the stepswhich comprise contacting a hydrocarbon mixture predominatinginsaturated straight chain hydrocarbons boiling within the gasolineboiling range with a catalyst melt comprising a molten mixture of halidesalts at least one of which is a halide of the Friedel- Crafts type in afirst reaction zone thereby e1- fccting the conversion of straight chainsaturated hydrocarbons to branched chain saturated hydrocarbons,continuously removing a portion of the catalyst melt from the firstreaction zone, contacting said portion of catalyst melt with saidhydrocarbon mixture passing to the first reaction zone therebyseparating active catalyst components from a fluid catalyst residue,adding a halide of the Friedel-Craits type to said catalyst residue, andcontacting at least apart of the efiluence of the first reaction zonecomprising branched chain saturated hydrocarbons together with an addedhydrocarbon fraction predomimating in olefinic hydrocarbons atalkylating conditions with said Friedel-Crafts type halidecontainingcatalyst residue in a second reaction zone thereby reacting branchedchain hydrocarbons with said olefinic hydrocarbons.

E. Ross.

